Polymerized catalyst composition

ABSTRACT

A composition is provided that includes a product of combining, in the presence of a free radical initiator a catalyst precursor and at least one monomer wherein the monomer and the catalyst precursor are poiymerizable by free-radical polymerization and wherein the catalyst precursor compound is represented by the formula: 
                         
wherein each X is an abstractable ligand; each R, R′, R″, R′″, R p1  and R p2  is independently hydrogen or a hydrocarbyl group provided at least one of R p1 , R p2,  and R′″ can be polymerized by a free radical initiator; and M is a Group-4-11 metal.

STATEMENT OF RELATED APPLICATIONS

This application claims priority from U.S. Ser. No. 60/421,282 filedOct. 25, 2002; U.S. Ser. No. 60/421,163 filed Oct. 25, 2002 and U.S.Ser. No. 60/421,164 filed Oct. 25, 2002. This application is related toU.S. Ser. No. 60/434,913 filed Dec. 20, 2002; U.S. Ser. No. 60/435,228filed Dec. 20, 2002; U.S. Ser. No. 60/435,046 filed Dec. 20, 2002; U.S.Ser. No. 60/433,934 filed Dec. 17, 2002; U.S. Ser. No. 60/434,082 filedDec. 17, 2002; and U.S. Ser. No. 60/446,607 filed Feb. 12, 2003.

FIELD OF THE INVENTION

This invention relates to methods of polymerizing or oligomerizing oneor more olefins using one or more activators with one or morepolymerized catalyst compounds prepared by polymerizing one or more freeradical polymerizable monomers (such as styrene) with one or moredifferent olefin polymerization catalyst precursor compounds containingterminal unsaturation.

BACKGROUND

U.S. Pat. No. 5,714,425 describes metallocene catalyst compositionshaving a polymerizable olefinic group. These metallocenes are describedas being useful to prepare polyolefins. In addition, these metallocenesare described as being polymerized with one or more alpha-olefins sothat the metallocene is copolymerized with the alpha-olefin. Thiscomposition is then described as useful to polymerize olefins. But U.S.Pat. No. 5,714,4254 does not disclose free-radical polymerization ofcatalyst compositions having a polymerizable olefinic group withmonomers such as styrene, isobutylene, 1,3-butadiene and the like.

U.S. Pat. No. 5,679,816 discloses biscyclopentadienyl transition-metalcomplexes containing a conjugated diene ligand group.

U.S. Pat. No. 6,150,544 and U.S. Pat. No. 6,352,953 disclose bimetallic,metallacyclic catalyst compounds where one metal is a Group-4 metal andthe other metal is a Group-3 metal. (Likewise, it is also known in theart to prepolymerize a heterogeneous catalyst system in the presence ofat least one olefin see EPA 426,646 and U.S. Pat. No. 4,871,705.)

SUMMARY

This invention relates to a composition comprising the product ofcombining, in the presence of a free radical initiator, one or moremonomers that can be polymerized by a free radical initiator and acatalyst precursor compound represented by the formula:

wherein each X is independently a C_(w) hydrocarbyl group or a halogen,and M is any Group-4-11 metal, a Group-8-9 metal, or Co or Fe. R, R′,and R″ are independently hydrogen or C_(x) to C_(y) hydrocarbyl groupsprovided that at least one R′ is capable of being polymerized in apolymerization process initiated by a free radical initiator.

This invention also relates to methods to polymerize olefins using theabove composition.

DETAILED DESCRIPTION

Definitions

The term “hydrocarbyl radical” is sometimes used interchangeably with“hydrocarbyl” throughout this document. For purposes of this disclosure,“hydrocarbyl radical” encompasses C₁-C₂₀₀ radicals. These radicals canbe linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic. Thus, the term “hydrocarbyl radical”, in addition tounsubstituted hydrocarbyl radicals, encompasses substituted hydrocarbylradicals, halocarbyl radicals, and substituted halocarbyl radicals, asthese terms are defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been replaced with a functional group such as NR″₂,OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the hydrocarbylradical, such as O, S, NR″, PR″, BR″, SiR″₂, GeR″₂, and the like, whereR″ is independently a C₁-C₃₀ hydrocarbyl or halocarbyl radical.Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen orhalogen-containing group (e.g. F, Cl, Br, I).

Substituted halocarbyl radicals are radicals in which at least onehydrocarbyl hydrogen or halogen atom has been substituted with afunctional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ andthe like or where at least one non-carbon atom or group has beeninserted within the halocarbyl radical such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like where R″ is independently a C₁-C₃₀hydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical.

In some embodiments, a hydrocarbyl radical is independently selectedfrom methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl,nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl,tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl,nonacosynyl, or triacontynyl isomers. The radical may then be subjectedto the types of substitutions described above.

Ancillary ligands serve to enforce the geometry around the metal center.

An “abstractable ligand” is a ligand that can be abstracted from themetal center by a cocatalyst leaving behind an activated catalyst. Forpurposes of this disclosure, an “abstractable ligand” does not containsulfur atoms; i.e. all abstractable ligands are non-sulfur-containingligands. For purposes of this disclosure oligomers have about 2-75 merunits. In some structures throughout this specification, drawing theligand-metal connection with an arrow, showing that the electrons forthe bond originally came from the ligand, sometimes indicatescoordination. At other times, drawing a solid line, showing the bond'scovalent nature, indicates coordination. One of ordinary skill in theart recognizes that these depictions are interchangeable.

The term “alkyl” or “alkyl radical” refers to a branched or unbranched,saturated or unsaturated, acyclic hydrocarbyl radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl). In particular embodiments, alkyls are C₁₋₂₀₀hydrocarbyls, C₁₋₅₀ hydrocarbyls, or C₁₋₂₀ hydrocarbyls.

Description

The inventive polymerized late transition metal catalyst precursors areprepared by copolymerizing Fe(II) or Co(II) pyridine diimine with anolefin such as styrene in the presence of a radical initiator (e.g.,AIBN). The pyridine diimine complexes contain aryl groups that aresubstituted with polymerizable olefinic substituents. Divinyl benzene isoptionally added to the copolymerization reaction medium to promotecross-linking.

Before polymerization into the polystyrene particle, the late transitionmetal catalyst precursors are sometimes simply called catalystprecursors. After polymerization, the catalyst precursors are sometimescalled polymerized catalyst precursors. After activation, thepolymerized catalyst precursors are sometimes called polymerizedcatalysts.

The inventive Fe(II) and Co(II) pyridine diimine complexes with olefinicsubstituents on aryl groups are synthesized. Then they are free-radicalcopolymerized with a simpler olefin. The resulting copolymer has unitsof polyolefin interspersed with enchained catalyst molecules (catalystprecursors).

In the presence of an activator, these enchained late transition metalcomplexes (catalyst precursors) function as ethylene polymerization oroligomerization catalysts. As shown in the Example section, arylsubstituents other than the olefinic substituent sometimes affectcatalyst performance.

Inventive late transition metal complexes are useful to preparecatalysts for olefin polymerization or oligomerization.

The above picture represents a schematic formula of the polymerizedcatalyst after polymerization. The P-labeled circles represent the bulkpolyolefin/catalyst polymer. The C-labeled circles represent thecatalyst.

More than one catalyst precursor compound may be polymerized with themonomers in varying ratios.

Catalyst Compounds

Catalyst compounds useful in this invention include those represented bythe formulas:

wherein each X is independently a hydrocarbyl group or a halogen,preferably a halogen, preferably chlorine; and M is any Group-4-11metal, Group-8-9, or Co or Fe.Useful Catalyst Compounds Include

-   2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-allylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-allylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-allylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(2-allylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    iron dichloride;    2-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    cobalt dichloride;    2-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    iron dibromide;    2-[1-(3-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    cobalt dibromide;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    iron dichloride;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    cobalt dichloride;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    iron dibromide;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-allylphenyliminoethyl]pyridine    cobalt dibromide;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(3-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(3-vinylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenyliminoethyl]pyridine    iron dichloride;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenyliminoethyl]pyridine    cobalt dichloride;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenyliminoethyl]pyridine    iron dibromide;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allylphenyliminoethyl]pyridine    cobalt dibromide;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(4-vinyl-2,6-diisopropylphenylimino)ethyl]-6-[1-(4-vinylphenylimino)ethyl]pyridine    cobalt dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dichloride;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    iron dibromide;    2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine    cobalt dibromide

The catalyst compounds described above may be prepared according toScheme I:

The first step in preparing invention catalysts is to prepare theancillary ligand. The ancillary ligand can be thought of as asubstituted pyridine. In Scheme I the pyridine substituents are eth-1-ylradicals that are themselves substituted. (For purposes of thisdisclosure, the naming convention “eth-1-yl” means that a ethyl radicalattaches to another group at the ethyl radical's 1 position; in manycases, the “-1-” portion can be omitted without loss of clarity.) Theethyl radicals substituted with an imino group; the imino group is alsosubstituted, this time with a phenyl or substituted phenyl group. Ageneral name for the ancillary ligand shown in Scheme I is2-[1-(2,6-dialkylphenylimino)ethyl]-6-[1-(4-allyl-2,6-dialkylphenylimino)ethyl]pyridine. Specifically, in Scheme I, the alkyl groupsare isopropyl groups.

As the name indicates, the pyridine is substituted at its 2 and 6positions: the square brackets set off the groups that substitute on thepyridine molecule. So, at the 2 position, pyridine is substituted withan ethyl-based radical: [1-(2,6-diisopropylphenylimino)ethyl]. Onceexplained, the parsing of the name leads straightforwardly to thestructure. The ethyl-based radical substitutes to the pyridine throughthe radical's 1 position. The ethyl-based radical is a substituted ethylradical. It is substituted at its 1 position by2,6-diisopropylphenylimino, which is an imino radical substituted with2,6-diisopropylphenyl.

Likewise, the substitution at the pyridine 6 position is[1-(4-allyl-2,6-diisopropyl phenylimino)ethyl]. This radical can beunderstood by going through the same parsing as described above. Theonly difference is in the phenyl group. Instead of being disubstituted,the phenyl-ring portion of the 6-position radical has an additionalallyl substitutent at the phenyl ring's 4 position.

Synthesis of the ligand can occur through coupling each of thesubstituted phenyl ring portions to the pyridine atom in such a way thatan iminoethyl connection occurs. One way of accomplishing this is shownin Scheme I. The coupling reaction is the acid-catalyzed addition of thesubstituted aniline to the carbonyl groups on the pyridine (with theloss of water).

Once both substituted anilines have been added to the pyridine,synthesis of the ancillary ligand is complete. After this the ligand issimply complexed with an appropriate dicationic transition metal halideby mixing the halide and the ligand together. Specifically, in Scheme I,this metal halide is iron (II) dichloride. Thus, the overall name of thecatalyst complex before it is copolymerized with an olefinic monomer is2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine iron dichloride

Process to Prepare the Polymerized Catalyst Compounds

The catalyst precursor compound described above is then contacted with afree radical initiator and one or more monomers that can be polymerizedby a free radical initiator. The catalyst compound containing theterminal unsaturation, as described above, is contacted with a freeradical initiator and one or more, free-radical-polymerizable monomers.

A typical late-transition metal catalyst is polymerized using thefollowing procedure. 50 ml of a toluene solution with theterminal-unsaturation-containing catalyst, styrene, and AIBN was kept at80° C. for 7 hrs. The resulting solution was evaporated and residue waswashed with dried mixture solution of hexane and toluene (2:1). Thesolid polymer product was collected. An analogous method was used forpreparation of other polymerized catalysts

The polymerization typically takes place in solution at a temperature of30-100° C., 50-90° C., 70-85° C., or 75-85° C. Suitable solvents includetoluene, benzene, xylene, and hexane. Desired solvents are selected fromthose that can dissolve the terminal unsaturation-containing catalyst.

The polymerization may be performed at atmospheric, sub-atmospheric orsuper-atmospheric pressures.

Generally, the structure of a catalyst will look like this beforecopolymerization.

Generally, the structure of a copolymer of a catalyst and an olefinlooks like this.

The polymerized catalyst compounds typically have Mw of up to 300,000;500-150,000; 1,000-100,000; 5,000-75,000; or 10,000-50,000.

Free Radical Initiators

Free radical initiators that are useful in this invention include: (1)thermally decomposable compounds which generate radicals such as azocompounds or organic peroxides; (2) compounds which generate freeradicals by non-thermal methods such as photochemical or redoxprocesses; (3) compounds which have inherent radical character such asmolecular oxygen; or (4) electromagnetic radiation such as X-rays,electron beams, visible light and ultraviolet-light. Suitable organicperoxide compounds include hydroperoxides, dialkyl peroxides, diacylperoxides, peroxyesters, peroxydicarbonates, peroxyketals, ketoneperoxides and organosulfonyl peroxides. Especially preferred peroxidesare t-butyl perbenzoate, dicumyl peroxide,2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (Lupersol 130),alpha,alpha.-bis(tert-butylperoxy)diisopropyl benzene (VulCup R).

Any free radical initiator or mixture having a 10-hour half-lifetemperature over 80° C. or their mixtures may function as the initiatorin invention processes to prepare supported polymerized catalystcompounds. Generally, the higher the decomposition temperature of theperoxygen compound, the better. See pages 66-67 of Modern Plastics,November 1971 for a more complete list of such compounds.

In one embodiment, the free radical initiator is an organic peroxidecompound having a half-life, at the reaction temperature, of less thanone tenth of the reaction/residence time employed. The free radicalinitiator is used at concentrations of 1-5% weight percent based onstyrene.

The following classes and examples of free-radical initiators are usefulin polymerizing invention terminal-unsaturation-containing catalystprecursor compounds:

Azo initiators Dialkyldiazenes 2,2′-azobis(2- methylpropanenitrile)(AIBN) 1,1-azobis(1- cyclohexanenitrile) 4,4′-azobis(4-cyanovalericacid) riphenylmethylazobenzene Hyponitrites di-t-butyl hyponitriteDicumyl hyponitrite Peroxides diacyl peroxides Dibenzoyl peroxideDidodecanoyl peroxide Diacetyl peroxide dialkyl peroxydicarbonatesDiisopropyl ester Dicyclohexyl ester Peresters alkyl hydroperoxidesCumyl hydroperoxide t-butyl hydroperoxide dialkyl peroxides Dicumylperoxide di-t-butyl peroxide inorganic peroxides Hydrogen peroxidepersulfate

Monomers Polymerizable by a Free Radical Initiator

Monomers that can be polymerized by a free radical process includeethylene, 1,3-butadiene, isoprene, styrene, alkyl styrene, isobutylene,vinyl chloride, vinylidene chloride, vinyl fluoride,tetrafluoroethylene, vinyl esters, acrylic esters, methacrylic esters,acrylonitrile, and propylene. Therefore, any of these can becopolymerized with the catalyst compound containing the terminalunsaturation. For example, selecting isoprene for copolymerizationresults in a catalyst/isoprene copolymer.

Process to Polymerize Olefins Using the Polymerized Catalyst Compound

Combining the polymerized catalyst compounds described above with one ormore activators forms an olefin-polymerization catalyst system.

For purposes of this disclosure, the terms activator and cocatalyst areused interchangeably. An activator functions to remove an abstractableligand X from the transition metal. After activation the transitionmetal is left with an empty coordination site at which incoming α-olefincan coordinate before it is incorporated into the oligomer or polymer.Any reagent that can so function without destroying the commercialviability of the oligomerization or polymerization process is suitablefor use as an activator or cocatalyst in this invention.

Invention-suitable activators include Lewis acid, non-coordinating ionicactivators or ionizing activators, or any other compound including Lewisbases, aluminum alkyls, conventional-type cocatalysts, and theircombinations that can convert a catalyst compound into a catalyticallyactive cation. This invention can use alumoxane or modified alumoxane asan activator, and can also use ionizing activators, neutral or ionic,such as tri (n-butyl) ammonium tetrakis(pentafluorophenyl) boron, atrisperfluorophenyl boron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, polyhalogenated heteroborane anions (WO98/43983), or their combinations. This invention can use these compoundsas activators if they can ionize the catalyst metal compound or if thecatalyst metal compound can be pre-reacted to form a compound that theseactivators can ionize.

One class of invention-suitable activators includes alumoxanes such asmethylalumoxane, modified methylalumoxane, ethylalumoxane, etc.;aluminum alkyls such as trimethyl aluminum, triethyl aluminum,triisopropyl aluminum, etc.; alkyl aluminum halides such as diethylaluminum chloride, etc.; and alkylaluminum alkoxides.

An alumoxane component useful as an activator is typically an oligomericaluminum compound represented by the general formula (R″—Al—O)_(n),which is a cyclic compound, or R″(R″—Al—O)_(n)AlR″₂, which is a linearcompound. Generally, R″ is independently a C₁-C₂₀ alkyl radical, forexample, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, etc.,and “n” is an integer from 1-50. Those of ordinary skill in the artrecognize that alumoxanes in which R″ is methyl and “n” is at least fourare particularly useful: methylalumoxane and modified methylalumoxanes.For further descriptions see, EP 279586, EP 561476, WO94/10180, and U.S.Pat. Nos. 4,665,208, 4,908,463, 4,924,018, 4,952,540, 4,968,827,5,041,584, 5,103,031, 5,157,137, 5,235,081, 5,248,801, 5,329,032,5,391,793, and 5,416,229.

Those of ordinary skill in the art know how to prepare alumoxanes andmodified alumoxanes. See U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352,5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031,5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656,5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publicationsEP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, andPCT publication WO 94/10180.

Another class of invention-suitable activators includes aluminum alkylcomponents represented by the general formula R″AlZ₂ where R″ is definedabove for alumoxanes, and each Z is independently R″ or a differentunivalent anionic ligand such as halogen (Cl, Br, I), alkoxide (OR″),etc. Particularly useful aluminum alkyls include triethylaluminum,diethylaluminum chloride, triisobutylaluminum, tri-n-octylaluminum, etc.

When alumoxane or aluminum alkyl activators are used, thecatalyst-precursor-to-activator molar ratio is from about 1:1000 to10:1; alternatively, 1:500 to 1:1; or 1:300 to 1:10.

Yet another class of invention-suitable activators includes discreteionic activators. These are especially useful when both abstractableligands are hydride or hydrocarbyl. [Me₂PhNH][B(C₆F₅)₄], [Bu₃NH][BF₄],[NH₄][PF₆], [NH₄][SbF₆], [NH₄][AsF₆], [NH₄][B(C₆H₅)₄] or Lewis acidicactivators such as B(C₆F₅)₃ or B(C₆H₅)₃ are examples of discrete ionicactivators. Discrete ionic activators provide for an activated catalystsite and a relatively non-coordinating (or weakly coordinating) anion.Activators of this type are well known, see for instance W. Beck, etal., Chem. Rev., vol. 88, p. 1405-1421 (1988); S. H. Strauss, Chem.Rev., vol. 93, p. 927-942 (1993); U.S. Pat. Nos. 5,198,401; 5,278,119;5,387,568; 5,763,549; 5,807,939; 6,262,202; and WO93/14132; WO99/45042;WO01/30785; and WO01/42249. These activator types also function when Xis not hydrocarbyl, if they are used with a compound capable ofalkylating the metal such as an alumoxane or aluminum alkyl.

When a discrete ionic activator is used, thecatalyst-precursor-to-activator molar ratio is from 10:1 to 1:10; 5:1 to1:5; 2:1 to 1:2; or 1.2:1 to 1:1.

Another class of invention-suitable activators includes those describedin PCT publication WO 98/07515 such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate. Combining activators from different classes suits thisinvention, for example, alumoxanes and ionizing activators incombinations, see for example, EP-B1 0 573 120, PCT publications WO94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410. WO98/09996 describes activating catalyst compounds with perchlorates,periodates, and iodates including their hydrates. WO 98/30602 and WO98/30603 describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate)•4THF as an activator for a catalystcompound. WO 99/18135 describes the use of organo-boron-aluminumactivators. EP-B1-0 781 299 describes using a silylium salt incombination with a non-coordinating compatible anion. Also, activationmethods using irradiation (see EP-B1-0 615 981), electrochemicaloxidation, etc., are also useful for activating catalyst precursors.Other activators or activating methods are described in, for example,U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide).

Combining modified alumoxanes with invention polymerized catalystcompounds forms a catalyst system. MMAO3A (modified methyl alumoxane inheptane, commercially available from Akzo Chemicals, Inc., Holland,under the trade name Modified Methylalumoxane type 3A) is such anexample. Combining the alumoxanes disclosed in U.S. Pat. No. 5,041,584with invention polymerized catalyst compounds forms a catalyst system,as well.

Polymerization Processes (TM Catalyzed)

Some of the catalyst systems described above are suitable for use insolution polymerization processes, some for use in gas-phase processes,and some in slurry processes. Some of the catalyst systems above aresuitable for use in combinations of those processes.

In invention polymerization or oligomerization processes using inventioncatalyst systems, the process temperature can be −100° C. to 300° C.,−20° C. to 200° C., or 0° C. to 150° C. Given one of these temperatureranges, the following ethylene oligomerization pressures (gauge) areuseful: 0 kPa-35 MPa or 500 kPa-15 MPa.

In polymerization or oligomerization processes using invention catalystsystems and any of the process conditions described above, whether theselected process is solution, slurry, gas-phase or an amalgamation ofthese, the process can employ one or more, C₂-C₃₀ monomers.Alternatively, C₂-C₁₂ or C₂-C₈ monomers are suitable. Specific examplesof invention-suitable monomers include one or more of ethylene,propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1,decene-1, 3-methyl-pentene-1, and cyclic olefins, or their combinations.Other monomers can include vinyl monomers, diolefins such as dienes,polyenes, norbornene, norbornadiene, vinyl norbornene, ethylidenenorbornene monomers. Alternatively, invention polymerization processesproduce homopolymers or copolymers of ethylene or propylene.

In polymerization or oligomerization processes using invention catalystsystems and any of the process conditions described above,polymerization with ethylene and at least two different comonomers formsterpolymers. Invention comonomers comprise a combination of any of themonomers described above or of C₂-C₃₀ or C4-C₈, α-olefin monomers,optionally with at least one diene monomer. Terpolymers includecombinations such as propylene/but-1-ene/hex-1-ene,propylene/but-1-ene/ethylene, propylene/ethylene/hex-1ene,propylene/butene/norbornene, propylene/butene/decadiene, and the like.For purposes of this disclosure, nomenclature such as “but-1-ene”, whichindicates that the olefinic unsaturation in the butene molecule beginsat the first atom in the butene carbon chain, is equivalent to“butene-1”.

Invention oligomerization or polymerization processes can be run in thepresence of various liquids, particularly aprotic organic liquids. Insome embodiments the catalyst system is insoluble in most solvents; andthus, the polymerization will be slurry phase rather than solutionphase. Liquid-suitable invention catalyst systems include alkanes,alkenes, cycloalkanes, selected halogenated hydrocarbons, aromatichydrocarbons, and in some cases, hydrofluorocarbons. Useful solventsspecifically include hexane, toluene, cyclohexane, and benzene.

Gas-phase Polymerization

In polymerization or oligomerization processes using invention catalystsystems, the reactor pressure in a gas-phase process can vary from 69kPa-3.5 MPa, alternatively from 690 kPa-3.5 MPa, from 1379 kPa-2.8 MPa,or from 1.7-2.414 MPa. Invention processes and catalyst systems can usesuitable gas-phase polymerization processes; some of these processes aredescribed below.

In gas-phase, polymerization or oligomerization processes usinginvention catalyst systems, given a particular reactor pressure range,the reactor temperature can vary from 30-120° C., alternatively from60-115° C., from 70-110° C., or from 70-95° C. The reactor temperatureis typically between 70-105° C. for high-density polyethylene.

In gas-phase systems, polymerization or oligomerization processes usinginvention catalyst systems, monomer partial pressure influences catalystsystem productivity. Primary monomer concentration, such as ethylene orpropylene, is from 25-90 mole percent, and its partial pressure is from138-517 kPa or 517 kPa-2.1 MPa. These conditions suit inventiongas-phase, polymerization or oligomerization processes. Also, in somesystems, comonomer presence yields productivity increases.

Gas-phase, polymerization or oligomerization processes using inventioncatalyst systems can produce 227-90,900 kg/hr of polymer, alternatively,227-455 kg/hr, 227-4540 kg/hr, 227-11,300 kg/hr, 227-15,900 kg/hr,227-22,700 kg/hr, and alternatively 29,000 kg/hr-45,500 kg/hr, or 45,500kg/hr or more.

Gas-phase, polymerization or oligomerization processes using inventioncatalyst systems can use the processes described in U.S. Pat. Nos.5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0 794200, EP-A-0 802 202 and EP-B-634 421.

In some gas-phase, polymerization or oligomerization processes usinginvention catalyst systems, the reactor receives the liquid or solutioncatalyst system in its liquid form at a resin-particle-lean zone. Forinformation on how to introduce a liquid catalyst system into afluidized bed polymerization reactor at a resin-particle-lean zone, seeU.S. Pat. No. 5,693,727.

Gas-phase, polymerization or oligomerization processes using inventioncatalyst systems can operate with scavengers. Typical scavengers includetrimethyl aluminum, tri-isobutyl aluminum, an excess of alumoxane ormodified alumoxane, triethylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, dibutyl zinc and the like. PCT publication WO96/08520 and U.S. Pat. No. 5,712,352 describe processes using thesescavengers. Invention, gas-phase processes or catalyst systems can usethese processes. Alternatively, gas-phase, polymerization, oroligomerization processes using invention catalyst systems can operatein the absence of or essentially free of scavengers.

Slurry Polymerization

In polymerization or oligomerization processes using invention catalystsystems, slurry polymerization processes generally use pressures of103-5068 kPa and temperatures of 0-120° C. Invention processes andcatalyst systems can use suitable slurry polymerization processes; someof these processes are described below.

Typically, in a slurry polymerization, a suspension of solid,particulate polymer forms in a liquid polymerization medium to whichethylene (or α-olefinic monomer) and comonomers, along with catalyst,has been added. This suspension intermittently or continuouslydischarges from the reactor, after which the process separates thepolymer from the volatile components and recycles them (optionally aftera distillation) to the reactor. The liquid employed in thepolymerization medium typically comprises a C₃-C₇ alkane, alternativelya branched alkane. The medium should be liquid and relatively inertunder the polymerization conditions. For propane media, processtemperatures and pressures are usually above the media's criticaltemperature and pressure. The processes can use hexane or isobutanemedia, as well.

One slurry polymerization process is a particle-form polymerization. Itis a process where the temperature remains below the temperature atwhich the polymer appreciably dissolves in the reaction medium. Suchtechniques are well known in the art. U.S. Pat. No. 3,248,179.Particle-form process temperatures range from 85° C.-110° C. Two otherslurry polymerization varieties employ a loop reactor or a plurality ofstirred reactors in series, parallel, or combinations thereof. Thesereactors can have cooling or not and can employ refrigerated orunrefrigerated monomer feeds. Non-limiting examples of slurry processesinclude continuous-loop and stirred-tank processes. Also, U.S. Pat. No.4,613,484 describes other examples of slurry processes.

Slurry processes can use a continuous-loop reactor. The processregularly injects the catalyst, as a slurry in a compatible solvent oras a dry, free-flowing powder, into the reactor loop. The loop containsa circulating slurry of growing polymer particles in a diluent ofisobutane containing monomer and comonomer. If desired, this process cancontrol molecular weight with hydrogen. The reactor is maintained at apressure of 3.620-4.309 kPa and at a temperature of 60-104° C. dependingon the desired polymer density. Reaction heat is removed from thereactor through the loop wall since much of the reactor vessel is adouble-jacketed pipe. The slurry discharges from the reactor at regularintervals or continuously. It discharges into a heated, low-pressureflash vessel, rotary dryer, and nitrogen purge column, in sequence, toremove isobutane diluent and all unreacted monomer and comonomer. Theresulting hydrocarbon-free powder is then compounded for use in variousapplications.

Polymerization or oligomerization processes using invention catalystsystems and using slurry polymerization conditions can produce 1-100,000kg polymer/hr, 907-100,000 kg/hr, 2268-100,000 kg/hr, 4540-100,000kg/hr, 6804-100,000 kg/hr, 11,340-100,000 kg/hr, or 45,500-100,000kg/hr.

Polymerization or oligomerization processes using invention catalystsystems and using slurry polymerization conditions can use total reactorpressures in the range of 2758-5516 kPa, 3103-4827 kPa, 3448-4482 kPa,or 3620-4309 kPa.

Polymerization or oligomerization processes using invention catalystsystems and using slurry polymerization conditions can useconcentrations of predominant monomer in the reactor liquid medium of1-10 wt %, 2-7 wt %, 2.5-6 wt %, or 3-6 wt %.

As with gas-phase polymerization conditions, polymerization oroligomerization processes using invention catalyst systems and slurrypolymerization conditions can use slurry process variants that includeor exclude scavengers.

Applications of Invention Polyolefins

Invention processes prepare homo- and co-polymer polyethylene useful forformulating adhesives and other materials.

Formulations

In some embodiments, the polymer produced by this invention may beblended with one or more other polymers such as thermoplastic polymer(s)and elastomer(s).

A thermoplastic polymer is a polymer that can be melted by heating andthen cooled without appreciable change in properties. Thermoplasticpolymers typically include polyolefins, polyamides, polyesters,polycarbonates, polysulfones, polyacetals, polylactones,acrylonitrile-butadiene-styrene resins, polyphenylene oxide,polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleicanhydride, polyimides, aromatic polyketones, or mixtures of two or moreof the above. Specific polyolefins include polymers comprising one ormore, linear, branched, or cyclic, C₂-C₄₀ olefins, preferably polymerscomprising ethylene or propylene copolymerized with one or more, C₃-C₄₀olefins, C₃-C₂₀ α-olefins, or C₃-C₁₀ α-olefins.

Elastomers include all natural and synthetic rubbers, including thosedefined in ASTM D1566. Examples of elastomers include ethylene propylenerubber, ethylene propylene diene monomer rubber, styrenic blockcopolymer rubbers (including SI, SIS, SB, SBS, SIBS and the like, whereS=styrene, I=isobutylene, and B=butadiene), butyl rubber, halobutylrubber, copolymers of isobutylene and para-alkylstyrene, halogenatedcopolymers of isobutylene and para-alkylstyrene, natural rubber,polyisoprene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, polybutadiene rubber (bothcis and trans).

In another embodiment polymer produced by this invention is combinedwith one or more isotactic polypropylenes; highly isotacticpolypropylenes; syndiotactic polypropylenes; random copolymers ofpropylene and ethylene or butene or hexene; polybutenes; ethylene vinylacetate; low-density polyethylenes (density 0.915 to 0.935 g/cm³);linear-low-density polyethylenes; ultra-low-density polyethylenes(density 0.86 to 0.90 g/cm³); very-low-density polyethylenes (density0.90 to 0.915 g/cm³); medium-density polyethylenes (density 0.935 to0.945 g/cm³); high-density polyethylenes (density 0.945 to 0.98 g/cm³);ethylene vinyl acetates; ethylene methyl acrylates; copolymers ofacrylic acid, polymethylmethacrylate, or any other polymerspolymerizable by high-pressure free radical processes;polyvinylchlorides, polybut-l-enes; isotactic polybutenes; ABS resins;ethylene-propylene rubbers (EPR); vulcanized EPRs; EPDMs; blockcopolymers; styrenic block copolymers; polyamides; polycarbonates; PETresins; crosslinked polyethylenes; copolymers of ethylene and vinylalcohol (EVOH); or polymers of aromatic monomers such as polystyrene;poly-1-esters; polyacetal; polyvinylidine fluoride; polyethyleneglycols; or polyisobutylenes.

In another embodiment, elastomers are blended with the polymer producedby this invention to form rubber-toughened compositions. In someembodiments, the rubber toughened composition is a two (or more) phasesystem where the elastomer is a discontinuous phase and the polymerproduced by this invention is a continuous phase. This blend may becombined with tackifiers or other additives as is known in the art.

In another embodiment, the polymer produced by this invention may beblended to form impact copolymers. In some embodiments, the blend is atwo (or more) phase system with a discontinuous phase and a continuousphase. This blend may be combined with tackifiers or other additives asis known in the art.

In some embodiments invention polymers are combined with metallocenepolyethylenes (mPEs) or metallocene polypropylenes (mPPs). The mPE andmPP homopolymers or copolymers are typically produced using mono- orbis-cyclopentadienyl transition metal catalysts in combination withalumoxane or a non-coordinating anion activator in solution, slurry,high-pressure, or gas-phase conditions. The supported or unsupportedcatalyst and activator may have substituted or unsubstitutedcyclopentadienyl rings. ExxonMobil Chemical Company (Baytown, Tex.)produces several commercial products with such catalyst and activatorcombinations. These are commercially available under the tradenamesEXCEED™, ACHIEVE™, and EXACT™. For more information on the methods andcatalyst-activator pairs used to produce such homopolymers andcopolymers, see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S.Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894;U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat.No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO91/09882; WO94/03506and U.S. Pat. No. 5,055,438.

In some embodiments invention polymers are present in the above blends,at from 10-99 wt %, 20-95 wt %, 30-90 wt %, 40-90 wt %, 50-90 wt %,60-90 wt %, 70-90 wt %. (Based upon the weight of the polymers in theblend.)

The blends described above may be produced by mixing the inventionpolymers with one or more polymers (as described above), by connectingreactors together in series to make reactor blends, or by using morethan one catalyst in the same reactor to produce multiple species ofpolymer. The polymers can be mixed together before being put into theextruder or may be mixed in the extruder.

Any of the above polymers may be functionalized, which means that thepolymer has been reacted with an unsaturated acid or anhydride.Unsaturated acids and anhydrides include any unsaturated organiccompound containing at least one double bond and at least one carbonylgroup. Representative acids include carboxylic acids, anhydrides, estersand their metallic and non-metallic salts. In some embodiments theorganic compound contains an ethylenic unsaturation conjugated with acarbonyl group (—C═O). Examples include maleic, fumaric, acrylic,methacrylic, itaconic, crotonic, alpha.methyl crotonic, and cinematicacids as well as their anhydrides, esters and salt derivatives. Theunsaturated acid or anhydride is present at 0.1-10 wt %, 0.5-7 wt % or1-4 wt %, based upon the weight of the hydrocarbon resin and theunsaturated acid or anhydride.

Tackifiers may be blended with invention polymers or with blends ofinvention polymers (as described above). Examples of useful tackifiersinclude aliphatic hydrocarbon resins, aromatic modified aliphatichydrocarbon resins, hydrogenated polycyclopentadiene resins,polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins,wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes,aromatic modified polyterpenes, terpene phenolics, aromatic modifiedhydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin,hydrogenated aliphatic aromatic resins, hydrogenated terpenes andmodified terpenes, and hydrogenated rosin esters. In some embodiments,the tackifier is hydrogenated. In other embodiments, the tackifier isnon-polar. (Non-polar means that the tackifier is substantially free ofmonomers having polar groups. Some tackifier compositions limit thepolar-group content to 5 wt % or less, alternatively, 2 or 0.5 wt % orless.) In some embodiments the tackifier has a softening point (Ring andBall, as measured by ASTM E-28) of 80-40 or 100-30° C. In someembodiments, the tackifier is functionalized, which means that thehydrocarbon resin has been contacted with an unsaturated acid oranhydride. Some embodiments select unsaturated acids or anhydrides fromany unsaturated organic compound containing at least one double bond andat least one carbonyl group. Representative acids include carboxylicacids, anhydrides, esters and their salts, both metallic andnon-metallic. In some embodiments the organic compound contains anethylenic unsaturation conjugated with a carbonyl group (—C═O). Examplesinclude maleic, fumaric, acrylic, methacrylic, itaconic, crotonic,alpha.methyl crotonic, and cinnamic acids as well as their anhydrides,esters and salt derivatives. The unsaturated acid or anhydride ispresent at 0.1 wt %, alternatively 0.5 wt % or 1 wt %, based upon theweight of the hydrocarbon resin and the unsaturated acid or anhydride.

Invention polymers, or their blends, may further comprise a crosslinkingagent. Particularly suitable crosslinking agents include those havingfunctional groups that can react with the acid or anhydride group.Alcohols, multiols, amines, diamines, and triamines belong to anonexclusive list of crosslinking agents. Examples of usefulcrosslinking agents include polyamines such as ethylenediamine,diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, andmenthanediamine.

Invention polymers, or their blends, may further comprise typicaladditives known in the art such as fillers, cavitating agents,antioxidants, surfactants, adjuvants, plasticizers, antiblock additives,color masterbatches, pigments, dyes, processing aids, UV stabilizers,neutralizers, lubricants, waxes, or nucleating agents. Typically, theseadditives are present in amounts well known to be effective in the art:such as 0.001-10 wt %.

Specific fillers, cavitating agents, or nucleating agents includetitanium dioxide, calcium carbonate, barium sulfate, silica, silicondioxide, carbon black, sand, glass beads, mineral aggregates, talc,clay, etc.

Effective antioxidants include phenolic antioxidants, such as Irganox1010, Irganox, 1076 both available from Ciba-Geigy. Effective oilsinclude paraffinic or naphthenic oils, such as Primol 352 or Primol 876available from ExxonMobil Chemical France, S.A. (Paris, France) andaliphatic naphthenic oils, white oils, etc.

Effective plasticizers and adjuvants include mineral oils, polybutenes,phthalates, etc. Plasticizers include phthalates such as diisoundecylphthalate (DIUP), diisononylphthalate (DINP), dioctylphthalates (DOP),and polybutenes.

Effective processing aids, lubricants, waxes, and oils include lowmolecular weight products such as wax, oil or low Mn polymer, (lowmeaning Mn below 5000, below 4000, below 3000, or below 2500). Effectivewaxes include polar or non-polar waxes, functionalized waxes,polypropylene waxes, polyethylene waxes, and wax modifiers. Effectivefunctionalized waxes include those modified with an alcohol, an acid, ora ketone.

Some invention polymers are functionalized after polymerization.Functionalized means that the polymer has been contacted with anunsaturated acid or anhydride. Suitable unsaturated acids or anhydridesinclude any unsaturated organic compound comprising one double bond andone carbonyl group. Representative acids include carboxylic acids,anhydrides, esters and their salts, both metallic and non-metallic. Someuseful organic compound contains an ethylenic unsaturation conjugatedwith a carbonyl group (—C═O). Examples include maleic, fumaric, acrylic,methacrylic, itaconic, crotonic, alpha.methyl crotonic, and cinnamicacids as well as their anhydrides, esters and salt derivatives. Theunsaturated acid or anhydride is present at 0.1-10 wt %, alternatively0.5-7 wt % or 1-4 wt % based upon the weight of the hydrocarbon resinand the unsaturated acid or anhydride. Specific examples include waxesmodified by methyl ketone, maleic anhydride, or maleic acid. Suitablelow Mn polymers include lower α-olefins polymers such as propylene,butene, pentene, hexene, etc. Some embodiments select the polymer suchthat it includes polybutene having an Mn of less than 1000.

Applications

Invention polymers (and their blends as described above) whether formedin situ or by physical blending are used in any known thermoplastic orelastomer application. Examples include uses in molded parts, films,tapes, sheets, tubing, hose, sheeting, wire and cable coating,adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elasticfibers, nonwoven materials, spunbond materials, sealants, surgicalgowns, and medical devices.

Adhesives

Invention polymers or their blends can be used as adhesives, eitheralone or combined with tackifiers. Preferred tackifiers are describedabove. The tackifier is typically present at about 1 wt % to about 50 wt%, based upon the weight of the blend, more preferably 10 wt % to 40 wt%, even more preferably 20 wt % to 40 wt %. Other additives, asdescribed above, may be added also.

Invention-polymer-based adhesives can be used in any adhesiveapplication, such as disposable items, packaging, laminates,pressure-sensitive adhesives, tapes labels, wood binding, paper binding,non-woven materials, road marking materials, reflective coatings, etc.In some embodiments Invention-polymer-based adhesives can be used forchassis construction in disposable diapers and napkins, elasticattachment in disposable-goods, and converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Specificarticles include diaper liquid-transfer layers, diaper leg elastics,diaper frontal tapes, diaper standing-leg cuffs, feminine-napkinadhesive strips and perishable product packaging. Specific applicationsinclude laminations for diaper outer covers, diaper elastic cuffs,filter materials, filter masks, surgical gowns, and surgical drapes;core stabilization for diapers and feminine-napkins; diaper chassisconstruction; and filtration system bonding.

The invention-polymer-based adhesives described above may be applied toany substrate. Useful substrates include wood, paper, cardboard,plastic, thermoplastic, rubber, metal, metal foil (such as aluminum foiland tin foil), metallized surfaces, cloth, non-woven cloth (particularlypolypropylene cloths), spunbonded fiber, cardboard, stone, plaster,glass (including silicon oxide (SiO_(x)) coatings applied by evaporatingsilicon oxide onto a film surface), foam, rock, ceramic, film, polymerfoam (such as polyurethane foam), coated substrate (such as those coatedwith inks, dyes, pigments), polyvinylidene chloride, etc. or theircombinations. Additional useful substrates include polyethylene,polypropylene, polyacrylates, acrylics, polyethylene terephthalate, orany of the polymers listed above as suitable for blends. Any of theabove substrates may be modified by corona treatment, electron beamirradiation, gamma irradiation, microwave, or silanization.

Films

Invention polymers and their blends can form mono- or multi-layer films.These films may be formed by any of the conventional techniques known inthe art including extrusion, co-extrusion, extrusion coating, andlamination, blowing and casting. These films may be formed by the flatfilm or tubular process; afterwards they may be oriented in a uniaxialor in two mutually perpendicular directions in the film's plane. One ormore of the layers of the film may be oriented in the transverse orlongitudinal directions to the same or different extents. Thisorientation may occur before or after bringing the individual layerstogether. For example, a polyethylene layer can be extrusion coated orlaminated onto an oriented polypropylene layer, or the polyethylene andpolypropylene can be coextruded into a film, then oriented. Likewise,oriented polypropylene could be laminated to oriented polyethylene ororiented polyethylene could be coated onto polypropylene. Furtherorientation could follow, if desired. Film orientation in the machinedirection (MD) is typically at a ratio of 1-15 or 5-7, while orientationin the transverse direction (TD) is typically at a ratio of 1-15 or 7-9.But in some embodiments, MD and TD orientation ratios are the same.

In another embodiment, the layer comprising the invention polymercompositions (or their blends) may be combined with one or more otherlayers. The other layer(s) may be any of those layers typically includedin multilayer films. For example, the other layer or layers may bepolyolefins (such as homopolymers or copolymers of C₂-C₄₀ olefins orC₂-C₂₀ olefins) or copolymers of α-olefins and other olefins (includingα-olefins and ethylene). Specific polyolefins for use as other layersinclude homopolyethylene; homopolypropylene; propylene copolymerizedwith ethylene or butene; and ethylene copolymerized with one or more ofpropylene, butene or hexene, and optional dienes. Specific examplesinclude thermoplastic polymers such as ultra-low-density polyethylene,very-low-density polyethylene, linear-low-density polyethylene,low-density polyethylene, medium-density polyethylene, high-densitypolyethylene, polypropylene, isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene, butene, hexene, elastomers such as ethylene propylenerubber, ethylene propylene diene monomer rubber, neoprene, and blends ofthermoplastic polymers and elastomers, such as for example,thermoplastic elastomers and rubber toughened plastics.

Likewise, the other layer or layers may be polar polymers. Specificpolar polymers include homopolymers and copolymers of esters, amides,acetates, anhydrides, copolymers of C₂-C₂₀ olefins (such as ethyleneand/or propylene and/or butene with one or more polar monomers such asacetates, anhydrides, esters, alcohol, or acrylics). Specific examplesinclude polyesters, polyamides, ethylene-vinyl-acetate copolymers, andpolyvinyl chloride.

Likewise, the other layer or layers may be cationic polymers. Specificcationic polymers include polymers or copolymers of geminallydisubstituted olefins, α-heteroatom-olefins, or styrenic monomers.Specific geminally disubstituted olefins include isobutylene,isopentene, isoheptene, isohexane, isooctene, isodecene, andisododecene. Specific α-heteroatom-olefins include vinyl ether and vinylcarbazole. Specific styrenic monomers include styrene, alkyl styrene,para-alkyl styrene, α-methyl styrene, chloro-styrene, andbromo-para-methyl styrene. Specific examples of cationic polymersinclude butyl rubber, isobutylene copolymerized with para methylstyrene, polystyrene, and poly-α-methyl styrene.

Finally, other specific layers can be paper, wood, cardboard, metal,metal foils (such as aluminum foil and tin foil), metallized surfaces,glass (including silicon oxide (SiO_(x)) coatings applied by evaporatingsilicon oxide onto a film surface), fabric, spunbonded fibers, andnon-wovens (particularly polypropylene spun bonded fibers ornon-wovens), and substrates coated with inks, dyes, pigments,polyvinylidene chloride and the like.

The films may vary in thickness depending on the intended application;films from 1-250 μm thick are usually suitable. Packaging films areusually from 10-60 μm thick. Sealing layers are typically 0.2-50 μm.There may be a sealing layer on both the inner and outer surfaces of thefilm or the sealing layer may be present on only the inner or the outersurface. Additives such as antiblock additives, antioxidants, pigments,fillers, processing aids, UV stabilizers, neutralizers, lubricants,surfactants and/or nucleating agents may also be present in one or morelayers in the films. Specific additives include silicon dioxide,titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calciumstearate, carbon black, low-molecular-weight resins, and glass beads. Insome embodiments one or more layers may be modified by corona treatment,electron beam irradiation, gamma irradiation, or microwave. In someembodiments one or both of the surface layers is modified by coronatreatment.

The films described herein may also comprise from 5-60 wt % of ahydrocarbon resin, based upon the weight of the polymer and the resin.The resin may be combined with the polymer of the seal layer(s) or maybe combined with the polymer in the core layer(s). The resin softeningpoint is 100-200° C. or 130-180° C. Preferred hydrocarbon resins includethose described above. The films comprising a hydrocarbon resin may beoriented in uniaxial or biaxial directions to the same or differentdegrees.

The films described above may be used as stretch or cling films.Stretch-cling films are used in various bundling, packaging andpalletizing operations. A number of well-known tackifying additivesimpart cling properties to or improve the cling properties of aparticular film. Common tackifying additives include polybutenes,terpene resins, alkali metal stearates, and hydrogenated rosins androsin esters. Corona discharge can also modify film properties. Somepolymers (such as ethylene-methylacrylate copolymers) do not need clingadditives and can be used as cling layers without tackifiers.Stretch-clings films may comprise a slip layer comprising any suitablepolyolefin or combination of polyolefins such as polyethylene,polypropylene, copolymers of ethylene and propylene, and polymersobtained from ethylene or propylene copolymerized with minor amounts ofother olefins, particularly C₄-C₁₂ olefins. Polypropylene and linear lowdensity polyethylene (LLDPE) work well. Suitable polypropylene isnormally solid and isotactic (greater than 90% hot heptane insolubles)and has wide ranging melt flow rates (0.1-300 g/10 min). Additionally,the slip layer may include one or more, anti-cling (slip or antiblock)additives that may be added during polyolefin production blended inafterwards to improve the layer's slip properties. Such additives arewell-known in the art and include, for example, silicas, silicates,diatomaceous earths, talcs, and various lubricants. These additives aretypically used in amounts ranging from 100-20,000 ppm or 500-10,000 ppmby weight based upon the weight of the slip layer. The slip layer may,if desired, also include one or more other additives as described above.

Polymer products can be used for nonwovens, sealing layers, orientedpolypropylene, and high-clarity thermoforming materials.

Low molecular weight varieties of high-pressure propylene homo- andco-polymers can be used for hot melt and pressure sensitive adhesives.

Invention processes can use finely divided, supported catalysts toprepare propylene/1-hexene copolymers with greater than 1.0 mole %hex-1-ene. In addition to finely divided supports, invention processescan use fumed silica supports in which the support particle size issmall enough to form a colloid in the reaction media.

End Use Articles

Laminates comprising invention polymers can be used as a thermoformablesheet where the substrate is either sprayed or injection molded tocouple it with the ionomer/tie-layer laminate sheet. The composite ifformed into the desired shape to form the article, or composite article.Various types of substrate materials to form highly desirable articles.The laminate can be used with plastic substrates such as homopolymers,copolymers, foams, impact copolymers, random copolymers, and otherapplications. Specifically, some articles in which the present inventioncan be incorporated are the following: vehicle parts, especiallyexterior parts such as bumpers and grills, rocker panels, fenders,doors, hoods, trim, and other parts can be made from the laminates,composites and methods of the invention.

Other articles can also be made, for example, counter tops, laminatedsurface counter tops, pool liners, pool covers, boat covers, boat sails,cable jacketing, motorcycles, snowmobiles, outdoor vehicles, marine boathulls, canoe interiors and exteriors, luggage, clothing, fabric(combined with non-wovens), tent materials, GORETEX, Gamma-radiationresistant applications, electronic housings (TV's, VCR's and computers),wood replacement for decks and other outdoor building materials, prefabbuildings, synthetic marble panels for construction, wall coverings,hopper cars, floor coating, polymer-wood composites, vinyl tiles, bath,shower, toilet applications and translucent glass replacement, sidings,lawn and outdoor furniture, appliances such as refrigerators, washingmachines, etc., child toys, reflective signage and other reflectivearticles on roads and clothing, sporting equipment such as snowboards,surfboards, skis, scooters, in-line skate wheels, scratch resistantCD's, stadium seats, aerospace reentry shields, plastic paper goods,sports helmets, plastic microwaveable cookware, and other applicationsfor coating plastics and metal where a highly glossy and scratchresistant surface is desirable, while not being subject to algae ordiscoloration.

Invention copolymers are suitable for applications such as moldedarticles, including injection and blow molded bottles and molded itemsused in automotive articles, such as automotive interior and exteriortrims. Examples of other methods and applications for making thesepolymers and for which these polymers may be useful are described in theEncyclopedia of Chemical Technology, by Kirk-Othmer, Fourth Edition,vol. 17, at pages 748-819. When the application is for molded articles,the molded articles may include a variety of molded parts, particularlymolded parts related to and used in the automotive industry, such as forexample bumpers, side panels, floor mats, dashboards and instrumentpanels. Foamed articles are another application and examples wherefoamed plastics, such as foamed polypropylene, are useful may be foundin Encyclopedia of Chemical Technology, by Kirk-Othmer, Fourth Edition,vol. 11, at pages 730-783. Foamed articles are particularly useful forconstruction and automotive applications. Examples of constructionapplications include heat and sound insulation, industrial, and homeappliances, and packaging. Examples of automotive applications includeinterior and exterior automotive parts, such as bumper guards,dashboards, and interior liners.

Invention polyolefin compositions are suitable for such articles asautomotive components, wire and cable jacketing, pipes, agriculturalfilms, geomembranes, toys, sporting equipment, medical devices, castingand blowing of packaging films, extrusion of tubing, pipes and profiles,sporting equipment, outdoor furniture (e.g., garden furniture) andplayground equipment, boat and water craft components, and other sucharticles. In particular, the compositions are suitable for automotivecomponents such as bumpers, grills, trim parts, dashboards andinstrument panels, exterior door and hood components, spoiler, windscreen, hub caps, mirror housing, body panel, protective side molding,and other interior and external components associated with automobiles,trucks, boats, and other vehicles.

Other useful articles and goods may be formed economically by thepractice of this invention include crates, containers, packaging,labware, such as roller bottles for culture growth and media bottles,office floor mats, instrumentation sample holders and sample windows;liquid storage containers such as bags, pouches, and bottles for storageand IV infusion of blood or solutions; packaging material includingthose for any medical device or drugs including unit-dose or otherblister or bubble pack as well as for wrapping or containing foodpreserved by irradiation. Other useful items include medical tubing andvalves for any medical device including infusion kits, catheters, andrespiratory therapy, as well as packaging materials for medical devicesor food which is irradiated including trays, as well as stored liquid,particularly water, milk, or juice, containers including unit servingsand bulk storage containers as well as transfer means such as tubing,pipes, and such.

EXAMPLES Catalyst Production Synthesis of 4-allyl-2,6-diisopropylaniline

A solution containing 2,6-diisopropyl aniline (35.4 g, 0.2 mol) andallyl chloride (7.6 g, 0.10 mol) was refluxed for 12 hr and then pouredinto water (400 ml). Adding an aqueous NaOH solution to the reactionmixture made the mixture basic. After extraction with diethyl ether(3×50 ml) and distillation (73.25 Pa, 92° C.), 18.33 g (84.3%) ofN-allyl-2,6-diisopropyl aniline was isolated. N_(d) ³⁰=1.5205. ¹H-NMR(ppm,CDCl₃): δ=7.10(d, 2H, Ph-Hm), 6.81(t, 1H, Ph-Hp), 6.05(m, 1H,CH═C), 5.34(d, 1H, C═C—H_(trans)), 5.16(d, 1H, C═C—H_(cis)), 3.71(broad,1H, NH), 3.50(d, 2H, CH₂—C═C), 3.26(m, 2H, CH(Me)₂), 1.28(d, 12H,C═C(CH₃)₂).

N-allyl-2,6-diisopropyl aniline (18.33 g, 0.084 mol) and ZnCl₂ (13.6 g,0.1 mol) were added to a 100 ml toluene solution. This solution wasrefluxed for 5 hr and then poured into a NaOH aqueous solution.Extraction with Et₂O (3×50 ml) and distillation (79.93 Pa, 98° C.)yielded 13.0 g (70.9%) of 4-allyl-2,6-diisopropyl aniline. N_(d)³⁰=1.5340, ¹H-NMR (ppm,CDCl₃): δ=6.85(s, 2H, Ph-Hm),5.98(m, 1H,CH═C),5.09(d, 1H, C═C—H_(trans)),5.03(d, 1H, C═C—H_(cis)),3.6(br, 2H,NH₂), 3.30(d, 2H, CH₂—C═C), 2.92(m, 2H, CH(Me)₂), 1.26(d, 12H, C(CH₃)₂)

Synthesis of2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine:Ligand I

2,6-diacetylpyridine (0.3 g, 1.84 mmol) and 2,6-diisopropylaniline(0.326, 1.84 mmol) were dissolved in 50 ml dry methanol. 2 ml formicacid was added as a catalyst, and the solution was stirred at roomtemperature for two days. The yellow solid (0.516 g, 87.1%) wascollected by filtration, washed with cold methanol, and identified asthe desired monoimine by ¹H-NMR. This monoimine (0.5 g, 1.55 mmol) wasdissolved in 25 ml hot methanol were added. 5 ml CH₂Cl₂, 2 ml formicacid, and excess 4-allyl-2,6-diisopropylaniline were then added to themonoimine. The solution was stirred in a sealed flask at 50° C. for 2days, and yielded 0.649 g (80.4%) yellow solid. ¹H-NMR (ppm, CDCl₃):8.46-8.50(br, 2H), 7.90-7.96(br, 1H), 7.17(d, 2H), 7.11(t, 1H), 6.98(s,2H), 6.05(br, 1H), 5.10(t, 2H), 3.41(d, 2H), 2.77(br, 4H), 2.27(s, 6H),1.14-1.17(br, 24H). IR(KBr cm⁻¹): 3078w, 2962s, 2926w, 2867w, 1639s,1567m, 1460s, 1365s, 1248m, 1209m, 1120s, 995w, 834m, 802w, 794w, 774w,737w.

Synthesis of2,6-bis[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine

A solution containing 2,6-diacetylpyridine (0.30 g, 1.84 mmol),4-allyl-2,6-diisopropylaniline (0.80 g, 3.68 mmol), and formic acid (2ml) in 30 ml dry methanol was refluxed under argon for 14 hours. Yellowsolid was collected by filtration and washed with cold methanol (3×5ml). Recrystallization from CH₂Cl₂:hexane (1:4) yielded 0.70 g (68%) ofyellow, 2,6-bis[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridinecrystals. IR (KBr): v(C═N) 1639 cm⁻¹. ¹H-NMR (CDCl₃): 8.47(d, 2H,Py-Hm), 7.92(t, 1H, Py-Hp), 6.98(s, 4H, Ph-Hm), 6.04(m, 2H, CH═C),5.12(m, 4H, C═CH₂), 3.40(d, 4H, CH₂—C═C), 2.75(m, 4H, CH(Me)₂), 2.27(s,6H, CH₃), 1.15(d, 24H, C(CH₃)₂); ¹³C-NMR(CDCl₃): 167.04(C═N),155.15(Py-C), 144.57(Ph-C), 138.12(Ph-C), 136.79(Py-C), 135.69(Ph-C),134.75(—CH═), 123.16(Py-C), 122.12(Ph-C), 115.34(═CH₂), 40.25(—CH₂—),28.31(C(Me)₂), 23.24(CH₃), 22.92(CH₃), 17.14(CH₃). C₃₉H₅₁N₃ (561.86g·mol-1): Anal. Calcd: C, 83.37; H, 9.15; N, 7.48. Found: C, 83.03; H,9.13; N, 7.55.

Synthesis f2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridineIminoDichloride: Catalyst I

2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridineiron dichloride was synthesized by adding FeCl₂.4H₂O to a THF solutionof Ligand I: 2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine.The complexing reaction proceeded with good yield. IR(KBr pellet):3074w, 2962s, 2926w, 2868w, 1637w, 1619w, 1584m, 1465s, 1370s, 1268m,1213m, 914m, 834w, 802w, 774m, 737w, 719w. EI-MS (70 eV): m/e=522(M+—FeCl2, 100%), 576(M+-2Cl, 20%).

Synthesis of2-[1-(phenylimino)ethyl]-6-[1-(4-allylphenylimino)ethyl]pyridine IronDichloride: Catalyst IA

This complex was prepared similarly to that of the diisopropyl analog(Catalyst I) except that unsubstituted aniline was used instead of2,6-diisopropyl aniline. This replacement occurs in the synthesis of the4-allyl-aniline and in the synthesis of the Ligand-I-typeiminoethyl-4-allyl-iminoethyl-pyridines, both of which are precursors tothis catalyst.

Synthesis of2-[1-(2,6-dimethylphenylimino)ethyl]-6-[1-(4-allyl-2,6-dimethylphenylimino)ethyl]pyridineIron Dichloride: Catalyst IB

This complex was prepared similarly to that of the diisopropyl analogexcept that 2,6-dimethyl aniline was used instead of 2,6-diisopropylaniline, as above. This replacement occurs in the synthesis of the4-allyl-aniline and in the synthesis of the Ligand-I-type liganddialkyliminoethyl-4-allyl-dialkyliminoethyl-pyridines, both of which areprecursors to this catalyst.

See Table 3 for an illustration of the behavior of Catalysts I-IB underpolymerization conditions.

Synthesis of2,6-bis[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine irondichloride: Catalyst II

A solution containing FeCl₂.4H₂O (0.20 g, 1.00 mmol) and2,6-bis[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine (0.60 g,1.07 mmol) in 40 ml THF was stirred for 5 hr and then evaporated in avacuum. The residue was washed with ether (3×10 ml), and recrystallizedfrom CH₂Cl₂:hexane (3:1) at −20° C. to afford blue crystals of2,6-bis[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine irondichloride (0.66 g, 95.9%). IR(KBr): v(C═N) 1621 cm⁻¹. EI-MS (70 eV):m/e 653(M+ —Cl, 10), 562(M+ —FeCl₂ 100), 520m+O—(FeCl₂—C₃H₆, 5).C₃₉H₅₁N₃FeCl₂ (688.61 g·mol⁻¹): Anal. Calcd: C, 68.03; H, 7.47; N, 6.10.Found: C, 67.70; H, 7.39; N, 6.13.

Catalyst Polymerization Preparation of Polymerized Late-transition Metal(Fe): Catalyst III

A solution containing2-[1-(2,6-diisopropylphenylimino)ethyl]-6-[1-(4-allyl-2,6-diisopropylphenylimino)ethyl]pyridine iron dichloride (Catalyst I) (0.50 g, 0.77mmol), styrene (4 ml) and AIBN (0.06 g) in 50 ml toluene was maintainedat 80° for 7 hrs. The resulting solution was evaporated, and theresulting residue was washed with a dried mixture of hexane and toluene(2:1). The solid polymer product was collected.

Preparation of Polymerized Late-transition Metal (Fe) Catalyst: CatalystIV

A solution containing2,6-bis[(4-allyl-2,6-diisopropylphenylamino)ethyl]pyridine irondichloride (Catalyst II) (0.34 g, 0.49 mmol), styrene (5 ml) and AIBN(0.20 g, 1.22 mmol) in 30 ml toluene was stirred, under argon, at 79-80°C. for 8 hr. The solution was evaporated under reduced pressure, and theresidue was washed with a hexane:toluene (2:1) solution to afford solidpolymerized catalyst: Catalyst IV. ICP-AES: 4.00 mg Fe/g poly.; GPC: Mw22598, Mn 15406, polydispersity index 1.47. ICP-AES was run with a TJAPOEMS ICP analyzer after dry ashing the product and dissolving it indilute nitric acid).

Olefin Polymerization

Ethylene polymerizations used toluene or hexane as the solvent and alsoused appropriate ethylene pressure. The polymerization vessel was a 500mL glass reactor equipped with a propeller-like stirrer. Solvent (100mL) was introduced into the argon-purged reactor and stirred (800 rpm).The solvent was heated to a prescribed polymerization temperature, andthen after, 20 minutes, an ethylene gas feed was started. Adding atoluene solution of cocatalyst (MMAO) and then catalyst (as solidparticles or dissolved in toluene) into the reactor with vigorousstirring (800 rpm) initiated polymerization. After a prescribed time,the ethylene gas feed was terminated. Alcohol (500 mL) and concentratedHCl (1 mL) were added to the resulting mixture. The polymer wascollected by filtration, washed with methanol (100 mL), and dried invacuum at 70° C. for 15 hours.

Ethylene polymerization using catalysts I and III in the presence ofMMAO dissolved in toluene under one atmosphere of ethylene wereinvestigated. Note that catalyst I is before the catalyst iscopolymerized with monomer (styrene), while catalyst III is aftercopolymerization with styrene. The results of ethylene polymerizationwere summarized:

TABLE 1 The Result of Ethylene Polymerization^(a) Catalyst III CatalystI Activity · Activity · 10⁻⁶ 10⁻⁶ n(Al)/n(Fe) (g PE/ M_(v) · (g PE/M_(v) · T(° C.) (molar ratio) mol · Fe · h) 10⁻⁴ mol · Fe · h) 10⁻⁴ 13550 1.033 15.74 0.644 23.43 13 1100 2.145 15.32 0.916 18.67 13 16502.233 11.17 0.959 18.21 13 2200 2.446 6.29 1.588 18.38 13 2750 2.3157.33 0.984 14.76 13 3300 1.912 6.25 0.627 11.15 −15 2200 5.948 20.593.750 24.11 0 2200 4.500 20.11 4.017 20.58 30 2200 2.112 5.46 1.262 8.6945 2200 1.314 4.92 0.860 8.44 60 2200 0.725 4.86 0.405 4.93 Toluenesolvent, 1atm of ethylene, reaction time 1 h.

TABLE 2 Aryl Substituent Effect on Catalyst Performance Activity, 10⁶ gCatalyst M R R′ PE/(mol · M · atm · hr) Mw I Fe ^(i)Pr ^(i)Pr 4.1 8.9 ×10⁴ Ia Fe H H Low MW Ib Fe Me Me Low MW

While certain representative embodiments and details have been shown toillustrate the invention, it will be apparent to skilled artisans thatvarious process and product changes from those disclosed in thisapplication may be made without departing from this invention's scope,which the appended claims define.

All cited patents, test procedures, priority documents, and other citeddocuments are fully incorporated by reference to the extent that thismaterial is consistent with this specification and for all jurisdictionsin which such incorporation is permitted.

Certain features of the present invention are described in terms of aset of numerical upper limits and a set of numerical lower limits. Thisspecification discloses all ranges formed by any combination of theselimits. All combinations of these limits are within the scope of theinvention unless otherwise indicated.

1. A composition comprising the product of combining, in the presence ofa free radical initiator, a catalyst precursor and at least one monomerwherein the monomer and the catalyst precursor are polymerizable byfree-radical polymerization and wherein the catalyst precursor compoundis represented by the formula:

wherein (a) each X is an abstractable ligand; (b) each R, R′, R″, R′″,R^(p1) and R^(p2) is independently hydrogen or a hydrocarbyl groupprovided at least one of R^(p1), R^(p2), or R′″ can be polymerized by afree radical initiator; (c) M is a Group-4-11 metal; and (d) at leastone of R′, R″, R′″, R^(p1) and R^(p2) is an allyl.
 2. The composition ofclaim 1 wherein each R, R′, R″, R′″, R^(p1) and R^(p2) are isindependently hydrogen or a C₁-C₅₀ hydrocarbyl group.
 3. The compositionof claim 2 wherein (a) each R′ is independently one of hydrogen, methyl,ethyl, propyl, butyl, cyclohexyl, phenyl; and (b) R^(p1) and R^(p2) areindependently hydrogen, methyl, ethyl, propyl, butyl, cyclohexyl,phenyl, vinyl, allyl, or ω-olefin provided that at least one of R^(p1)and R² can be polymerized by a free radical initiator.
 4. Thecomposition of claim 2 wherein (a) each R is independently one ofhydrogen, allyl, methyl, or phenyl; (b) each R″ is independently one ofhydrogen, methyl, or phenyl; (c) each R′″ is independently one ofhydrogen, methyl, isopropyl, tertiary butyl, or phenyl.
 5. Thecomposition of claim 3 wherein (a) each R is independently one ofhydrogen, allyl, methyl, or phenyl; (b) each R″ is independently one ofhydrogen, methyl, or phenyl; (c) each R′″ is independently one ofhydrogen, methyl, isopropyl, tertiary butyl, or phenyl.
 6. Thecomposition of claim 3 wherein M is selected from a Group 8 or 9transition metal.
 7. The composition of claim 6 wherein M is selectedfrom Fe or Co.
 8. The composition of claim 3 wherein the abstractableligands, X are independently hydride radicals; hydrocarbyl radicals orhydrocarbyl-substituted organometalloid radicals.
 9. The composition ofclaim 8 wherein two abstractable ligands, X, join to form a 3-to-40-atommetallacycle ring.
 10. The composition of claim 8 wherein abstractableligands, X are independently halogen, alkoxide, aryloxide, amide, orphosphide radicals.
 11. The composition of matter of claim 10 whereinabstractable ligands X, are independently chloride, bromide, iodide,methoxy, ethoxy, propoxy, butoxy, dimethylamino, diethylamino,methylethylamino, phenoxy, and benzoxy.
 12. The composition of matter ofclaim 11 wherein at least one abstractable ligand is chloride.
 13. Thecomposition of claim 3 wherein the one or more monomers comprisestyrene, vinyl styrene, alkyl styrene, isobutylene, isoprene, orbutadiene.
 14. The composition of claim 13 wherein the one or moremonomers comprise styrene.
 15. The composition of claim 3 wherein thefree radical initiator is azo initiators or peroxides.
 16. Thecomposition of claim 3 wherein the free radical initiator isdialkyldiazenes, hyponitrites, diacyl peroxides, dialkylperoxydicarbonates, peresters, alkyl hydroperoxides, dialkyl peroxides,or inorganic peroxides.
 17. The composition of claim 3 wherein the freeradical initiator is selected from 2,2′azobis(2-methylpropanenitrile),1,1-azobis(1-cyclohexanenitrile), 4,4′-azobis(4-cyanovaleric acid),triphenylmethylazobenzene, di-t-butyl hyponitrite, dicumyl hyponitrite,dibenzoyl peroxide, didodecanoyl peroxide, diacetyl peroxide,diisopropyl ester, dicyclohexyl ester, cumyl hydroperoxide, t-butylhydroperoxide, dicumyl peroxide, di-t-butyl peroxide, hydrogen peroxide,and persulfate initiators.
 18. A catalyst system comprising the reactionproduct of the composition of claim 1 and an activator.
 19. The catalystsystem of claim 18 wherein the activator is selected from alumoxanes,aluminum alkyls, alkyl aluminum halides, alkylaluminum alkoxides,discrete ionic activators, and Lewis acid activators.
 20. The catalystsystem of claim 19 wherein the activator is selected frommethylalumoxane, modified methylalumoxane, ethylalumoxane, trimethylaluminum, triethyl aluminum, triisopropyl aluminum, diethyl aluminumchloride, alkylaluminum alkoxides, ammonium borate salts, phosphoniumborate salts, triphenyl carbenium borate salts, ammonium aluminatesalts, phosphonium aluminate salts, triphenyl carbenium aluminate salts,trisarylborane acids, and polyhalogenated heteroborane anions.
 21. Amethod to polymerize olefin comprising contacting an olefin and thecomposition of any of claims 1-17.
 22. The catalyst system of any ofclaims 18, 19 or 20 and an olefin.